US4346014A - Rolling oil compositions and method of inhibiting carbon smut on batch annealed steel - Google Patents
Rolling oil compositions and method of inhibiting carbon smut on batch annealed steel Download PDFInfo
- Publication number
- US4346014A US4346014A US06/255,605 US25560581A US4346014A US 4346014 A US4346014 A US 4346014A US 25560581 A US25560581 A US 25560581A US 4346014 A US4346014 A US 4346014A
- Authority
- US
- United States
- Prior art keywords
- dinitro
- sup
- benzoic acid
- weight
- rolling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010731 rolling oil Substances 0.000 title claims abstract description 45
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 39
- 239000010959 steel Substances 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 title claims description 13
- 230000002401 inhibitory effect Effects 0.000 title description 5
- 238000005097 cold rolling Methods 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 10
- 239000010960 cold rolled steel Substances 0.000 claims abstract 2
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 dimethyl octyne diol ester Chemical class 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 14
- YKMDNKRCCODWMG-UHFFFAOYSA-N 2,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC=C1[N+]([O-])=O YKMDNKRCCODWMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 6
- 229920001522 polyglycol ester Polymers 0.000 claims description 6
- MKWJZTFMDWSRIH-UHFFFAOYSA-N (4-fluoro-3-nitrophenyl)methanol Chemical compound OCC1=CC=C(F)C([N+]([O-])=O)=C1 MKWJZTFMDWSRIH-UHFFFAOYSA-N 0.000 claims description 4
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 4
- VILFTWLXLYIEMV-UHFFFAOYSA-N 1,5-difluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(F)C=C1F VILFTWLXLYIEMV-UHFFFAOYSA-N 0.000 claims description 4
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims description 4
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 claims description 4
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 claims description 4
- GPNAVOJCQIEKQF-UHFFFAOYSA-N 6-nitro-1,3-benzothiazol-2-amine Chemical compound C1=C([N+]([O-])=O)C=C2SC(N)=NC2=C1 GPNAVOJCQIEKQF-UHFFFAOYSA-N 0.000 claims description 4
- ZIIGSRYPZWDGBT-UHFFFAOYSA-N 610-30-0 Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O ZIIGSRYPZWDGBT-UHFFFAOYSA-N 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 44
- 229910021529 ammonia Inorganic materials 0.000 description 22
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- 239000007921 spray Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 5
- 239000007764 o/w emulsion Substances 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000010292 orthophenyl phenol Nutrition 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- WCWCXXCPWVJBSH-UHFFFAOYSA-N 4-methylnon-2-yne Chemical compound CCCCCC(C)C#CC WCWCXXCPWVJBSH-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- PADMMUFPGNGRGI-UHFFFAOYSA-N dunnite Chemical compound [NH4+].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O PADMMUFPGNGRGI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 229920000847 nonoxynol Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000002888 oleic acid derivatives Chemical class 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- LBWCDROIOCXGGV-UHFFFAOYSA-N 2-(1,3,5-triazin-2-yl)ethanol Chemical compound OCCC1=NC=NC=N1 LBWCDROIOCXGGV-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- NCKMMSIFQUPKCK-UHFFFAOYSA-N 2-benzyl-4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1CC1=CC=CC=C1 NCKMMSIFQUPKCK-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WTWGHNZAQVTLSQ-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WTWGHNZAQVTLSQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229940095098 glycol oleate Drugs 0.000 description 1
- 229940100242 glycol stearate Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000059 polyethylene glycol stearate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
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- C—CHEMISTRY; METALLURGY
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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
Definitions
- red hot steel slabs are hot reduced in one or several steps into a steel band of about 1/4" thickness.
- a heavy mill scale of iron oxides forms on the steel which has to be removed by acid pickling.
- This operation leads to considerable losses of metal from the surface.
- the surface area is increased manyfold and hot rolling becomes impractical. Therefore, the hot band is reduced further by cold rolling.
- it is essential to employ a rolling oil to reduce friction and to facilitate a larger cross sectional reduction.
- Cold rolling of carbon steel introduces work hardening, which can be considerable in modern multi-stand mills.
- Too much hardening renders the sheet metal unsuitable for further forming operations, be it tight bending, deep drawing, punching or further gauge reduction.
- the steel has to be annealed by heating it for about 10 to 12 hours to temperatures between 1000° and 1400° F. in a reducing atmosphere.
- the rolling oil is usually left on the steel, partly for rust protection for the time in storage prior to anneal, but mainly because of the expense in removing it.
- Cleaning steel is costly because it requires extra process equipment. It cannot be done in-line with the rolling operation because cleaning requires considerably more time than rolling. Occasionally, a mill cleaner is applied in line but because of the high speed, only marginal cleaning is achieved, i.e. an oil film from the rolling oil remains on the steel.
- the steel sheet, rolled up in large coils, is annealed with an oily surface.
- Modern rolling oils are mixtures of many different compounds. They are normally applied from a water based emulsion in concentrations from 0.5 to 15%.
- the main ingredients are mineral oils (i.e. hydrocarbons), fatty oils and greases (i.e. polyalcohol esters of fatty acids), and fatty amides.
- Other additives are present which are necessary for a satisfactory performance, such as detergents, emulsifiers, fungicides, bactericides, antioxidants and high pressure lubricant additives. None of these compounds is stable at a temperature above 1000° F. In air, they simply burn off. In the reducing atmosphere used in the annealing chamber, the rolling oil decomposes.
- carbon smut Some of it is distilled off, but enough of it breaks down into gaseous products and higher weight materials which finally end up as a carbonaceous layer on the steel surface called carbon smut.
- the amount of carbon smut deposit and its structure depends on many parameters, i.e. composition of the rolling oil, type of steel, rate of heatup, duration of heat cycle while annealing, peak temperature and type of annealing gas. In most cases, the presence of carbon smut on the steel surface is detrimental for later surface treatments.
- the organic nitro compounds are one or more members selected from the group consisting of 2,4-dinitro benzoic acid, 2,5-dinitro benzoic acid, 3,4-dinitro benzoic acid, 3,5-dinitro benzoic acid, picric acid, 1,3-dinitro benzene, 2,4,6-trinitro toluene, 3,5-dinitro salicylic acid, 2-amino-6-nitrobenzothiazole, poly glycol ester of 3,5-dinitro benzoic acid, dimethyl octyne diol ester of 3,5-dinitro benzoic acid, 2,4,7-trinitro-9-fluorenone and 1,5-difluoro-2,4-dinitro benzene.
- the processed steel may have additional surface treatments following annealing.
- Another aspect of our invention is directed to a cold rolling lubricant composition
- a cold rolling lubricant composition comprising a conventional rolling oil which contains from 0.5 to 5% of one or more of the additives described above which inhibit the formation of carbon smut when the steel is batch annealed.
- the rolling oil containing the smut inhibiting additive may be used undiluted in the cold rolling mill but generally it is used as an oil in water emulsion with the oil constituting from about 0.5 to 15% by weight of the combined oil and water.
- the chemicals which we add to conventional rolling lubricant to inhibit the formation of carbon smut during batch annealing are one or more members selected from the group consisting of 2,4-dinitro benzoic acid, 2,5-dinitro benzoic acid, 3,4-dinitro benzoic acid, 3,5-dinitro benzoic acid, picric acid, 1,3-dinitro benzene, 2,4,6-trinitro toluene, 3,5-dinitro salicylic acid, 2-amino-6-nitrobenzothiazole, poly glycol ester of 3,5-dinitro benzoic acid, dimethyl octyne diol ester of 3,5-dinitro benzoic acid, 2,4,7-trinitro-9-fluorenone and 1,5-difluoro-2,4-dinitro benzene.
- the smut inhibiting additives are incorporated into the cold rolling oil in an amount ranging from about 0.5 to 5% by weight based on the combined weight of the additive and rolling oil. In some cases, we have found 0.5% of the organic nitro compound to be an effective smut inhibitor but we prefer a minimum of about 1%. Amounts greater than 5% give no increased benefit.
- the smut inhibiting additives as well as other additives described below are easily incorporated in the cold rolling oil by conventional liquid mixing and blending equipment.
- organic nitro compounds which are effective smut inhibitors are either soluble in the rolling oil or are soluble in the water used to prepare oil in water emulsions which are then used as the rolling lubricant.
- the cold rolling oil can be any conventional rolling oil available on the market today from a large number of suppliers.
- the cold rolling oil will be based on a mineral oil derived from either a naphthenic or paraffinic base.
- the mineral oil may vary from about 0 to 95% by weight of the rolling lubricant.
- the mineral oil will generally have a viscosity range of 150 to 350 S.U.S.
- the rolling lubricant will generally have present from about 0 to 95% by weight of fatty acid esters such as tallow, white or yellow grease and lard derived primarily from oleic, palmitic and stearic acid esters of glycerol.
- the mineral oil and fatty acid esters in total must comprise at least about 80% by weight of the cold rolling oil. Either one or any mixture of the mineral oil and fatty acid ester totalling at least about 80% by weight of the rolling lubricant is satisfactory.
- fatty acids may also be present such as tallow fatty acids and tall oil fatty acids composed primarily of oleic, stearic or palmitic fatty acids.
- the fatty acids will constitute about 0 to 10% by weight of the rolling lubricant.
- the cold rolling oil or lubricant may also contain from about 0.1 to 0.5% antioxidants such as 2,6 di-tertiary butyl phenol; 2,6 di-tertiary butyl 4-n-butyl phenol; 2,6 di-tertiary butyl p-cresol; 4-hydroxymethyl 2,6 di-tertiary butyl phenol; butylated hydroxytoluene or 2,2' methylenebis (4-methyl 6-tert butylphenol).
- antioxidants such as 2,6 di-tertiary butyl phenol; 2,6 di-tertiary butyl 4-n-butyl phenol; 2,6 di-tertiary butyl p-cresol; 4-hydroxymethyl 2,6 di-tertiary butyl phenol; butylated hydroxytoluene or 2,2' methylenebis (4-methyl 6-tert butylphenol).
- a bactericide such as orthophenyl phenol; 2,4,5 trichlorophenol; pentachlorophenol; o-benzyl p-chlorophenol; or hexahydro-1,3,5 tris(2-hydroxyethyl-S-triazine) is very desirable and in many cases necessary.
- Perfumes at a concentration of about 0.1 to 0.3% by weight and defoaming agents at a concentration of about 0.05 to 1.0% by weight may also be present.
- Typical defoaming agents include dimethyl silicone and dimethyl polysiloxane as well as many others of undisclosed composition.
- a typical cold rolling oil or rolling lubricant will have the following composition expressed as percent by weight: mineral oil--45%, yellow grease--44%, smut inhibitor (2,4,6-trinitrotoluene)--1%, fatty acid (tallow fatty acid)--4%, emulsifier (nonylphenol ethoxylate)--5.7%, antioxidant (2.6-ditertiarybutylphenol)--0.1%, perfume--0.1%, bactericide (o-phenylphenol)--0.05% and defoamer (silicone fluid)--0.05%.
- the rolling oils with the 0.5 to 5% by weight of organic nitro compound smut inhibitor may be used neat but generally for economic reasons the rolling oils are used as oil in water emulsions.
- the amount of rolling oil emulsified in water will vary from about 0.5 to 15% by weight based on the combined weight of the oil and water.
- the oil in water emulsion can be prepared by adding the rolling oil to the water in a mixing tank using a high speed stirrer. In order to prepare the oil in water emulsion it is necessary that an emulsifying agent be present in the rolling oil at a concentration of about 0.5 to 10% by weight. If desired, the emulsifying agent can be added to the water used to prepare the oil in water emulsion.
- the emulsifier used in preparing the oil in water emulsion can be any conventional emulsifying agent.
- Typical emulsifying agents are the ethoxylated alkyl phenols in which the alkyl groups may be within the range of C 8 to C 18 and the moles of ethylene oxide range from 5 to 12 units.
- Typical ethoxylated alkyl phenols are octy phenol, nonyl phenol, dodecyl phenol and dinonyl phenol ethoxylates.
- emulsifiers useful in our invention is the ethoxylated linear and branched chain primary alcohols of C 8 to C 16 carbon content and having about 5 to 12 moles of ethylene oxide per mole of alcohol.
- Tridecyl alcohol ethoxylate is an example.
- emulsifiers are the ethoxylated fatty amines of C 11 to C 18 and having about 5 to 15 moles of ethylene oxide per mole of fatty amine.
- examples of this class of emulsifier are oleyl amine, octadecyl amine and coco amine ethoxylates.
- the polyethylene oxide glycol esters of C 12 to C 18 fatty acids having about 5 to 15 moles of ethylene oxide per mole of fatty acid are also good emulsifiers for oil in water emulsions.
- This class of emulsifiers includes polyoxyethylene glycol oleate (5 to 15 moles of ethylene oxide, polyoxyethylene glycol stearate (5 to 15 moles of ethylene oxide) and polyoxyethylene glycol laurate (5 to 15 moles ethylene oxide).
- the pH of the aqueous emulsion must be within the range of about pH 4 to 8.
- acidic components such as by using nitrated benzoic acid or nitrated salicylic acid smut inhibitors or by using acidic emulsifying agents an alkaline type pH modifier is required.
- the rolling oil will contain about 0 to 8% by weight of the pH modifier. The percent by weight of the pH modifier is determined largely by trial and error experiments.
- aliphatic amines of C 2 to C 12 range to be satisfactory pH modifiers.
- Typical amines are morpholine, di-n-butylamine, di-n-propylamine and di-hexylamine; useful aromatic amines are aniline, pyridine and diphenylamine.
- a typical rolling oil containing a carbon smut inhibitor together with a pH modifier has the following composition expressed as percent by weight: Blend of palmitic, stearic and oleic acid esters of glycerol--67%; paraffinic mineral oil (200 SUS)--22.9%; blends of palmitic, stearic and oleic acids (fatty acid)--5.5%; nonyl phenol ethoxylate (9 moles EO) (emulsifier)--2.2%; 3,5 dinitro benzoic acid (smut inhibitor)--1.0%; morpholine (pH modifier)--1.0%; o-phenyl phenol (biocide)--0.2%; butylated hydroxytoluene (antioxidant)--0.1%; and odor masking perfume--0.1%. (Total--100%).
- Each of the rolling oil compositions as prepared in Example I is emulsified in water at 10% by volume to provide an emulsion having a concentration which will yield and oil coating weight on steel approximately equal to that obtained under production conditions.
- Steel test panels are dipped in each 10% emulsion until thoroughly coated and then supported vertically on paper towels until the water has evaporated, leaving an oil coating on the steel.
- These prepared panels are then stacked and bolted between two steel plates after which they are stored overnight at 250° F. to simulate a tightly wound steel coil from a rolling mill.
- this stack of panels is placed in an inert gas atmosphere retort furnace of 6 liter volume.
- the gas used is 95% nitrogen/5% hydrogen at a flow rate of 300 cc. per minute.
- the steel panels were annealed in this furnace at 1250° F. for 10 hours. After cooling, the panels were observed visually.
- the panels were rated for amount of smut by visual inspection. For each variation, sets of 6 panels were prepared. Up to 11 sets could be tested in one stack. In each annealing run, one control set of oiled panels without additives was included as a control, against which the sets with additives were rated. It is not possible to attach absolute numerical values to the visual appearance, because the quality of steel as manufactured in a mill does vary enough from batch to batch, even for the same grade of steel to result in differences in appearance. We made reasonably sure that we at least used the same batch of steel for one run and judged the appearance of the sets relative to each other. The observations of smut inhibition are shown in Table I below.
- the panels were cleaned in a commercial heavy duty alkaline cleaner at 200° F. temperature and of 8 oz/gal concentration by brushing and 1 minute immersion.
- the panels were water rinsed and spray coated 1 minute at 135° F. with a commercial zinc phosphate coating bath of 12 points concentration.
- a commercial zinc phosphate coating bath of 12 points concentration.
- Such a bath consists essentially of a water solution of about 1% of acid zinc phosphate with minor amounts of acid nickel phosphate and nitric acid, operated at a pH close to the precipitation point of tertiary zinc phosphate.
- each panel was scored with a steel scribe down to metal by making two lines diagonally from corner to opposite corner.
- the panels were then placed in a salt spray cabinet and exposed to salt spray for 10 days at 95° F. and a salt concentration of 5%, according to test method ASTM B117.
- the panels were rated for the width of corrosion creep from the scribe line according to ASTM D1654.
- a rating below 6 is usually considered failing, although for some inexpensive low cost finishes, figures even as low as 4 might be acceptable. Results of 8 (1/32" creep) and higher are considered excellent.
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Abstract
Carbon smut on post-annealed cold rolled steel sheet and strip is inhibited by a process using a rolling oil containing from 0.5 to 5% by weight of specific organic nitro compounds in the cold rolling oil. The steel sheet and strip are substantially smut free after batch annealing. Rolling oils and their aqueous emulsions containing the organic nitro inhibitors are also disclosed and claimed.
Description
In the manufacturing of automotive and appliance grade steel sheet and strip, red hot steel slabs are hot reduced in one or several steps into a steel band of about 1/4" thickness. In this operation, a heavy mill scale of iron oxides forms on the steel which has to be removed by acid pickling. This operation leads to considerable losses of metal from the surface. For further reduction, the surface area is increased manyfold and hot rolling becomes impractical. Therefore, the hot band is reduced further by cold rolling. For this step, it is essential to employ a rolling oil to reduce friction and to facilitate a larger cross sectional reduction. Cold rolling of carbon steel introduces work hardening, which can be considerable in modern multi-stand mills. Too much hardening renders the sheet metal unsuitable for further forming operations, be it tight bending, deep drawing, punching or further gauge reduction. To remove the excess hardness, the steel has to be annealed by heating it for about 10 to 12 hours to temperatures between 1000° and 1400° F. in a reducing atmosphere.
After the cold rolling step, the rolling oil is usually left on the steel, partly for rust protection for the time in storage prior to anneal, but mainly because of the expense in removing it. Cleaning steel is costly because it requires extra process equipment. It cannot be done in-line with the rolling operation because cleaning requires considerably more time than rolling. Occasionally, a mill cleaner is applied in line but because of the high speed, only marginal cleaning is achieved, i.e. an oil film from the rolling oil remains on the steel. Usually the steel sheet, rolled up in large coils, is annealed with an oily surface.
Modern rolling oils are mixtures of many different compounds. They are normally applied from a water based emulsion in concentrations from 0.5 to 15%. The main ingredients are mineral oils (i.e. hydrocarbons), fatty oils and greases (i.e. polyalcohol esters of fatty acids), and fatty amides. Other additives are present which are necessary for a satisfactory performance, such as detergents, emulsifiers, fungicides, bactericides, antioxidants and high pressure lubricant additives. None of these compounds is stable at a temperature above 1000° F. In air, they simply burn off. In the reducing atmosphere used in the annealing chamber, the rolling oil decomposes. Some of it is distilled off, but enough of it breaks down into gaseous products and higher weight materials which finally end up as a carbonaceous layer on the steel surface called carbon smut. The amount of carbon smut deposit and its structure depends on many parameters, i.e. composition of the rolling oil, type of steel, rate of heatup, duration of heat cycle while annealing, peak temperature and type of annealing gas. In most cases, the presence of carbon smut on the steel surface is detrimental for later surface treatments.
Most of the steel sheet is used for manufacturing products that will later receive an organic finish such as a paint or polymer coating. To get a useful life out of a paint coat, a proper surface preparation is essential. This mostly requires a conversion coating based on phosphates, which acts as an adhesion promoter and corrosion stopper in case of physical damage to the paint. Phosphate coatings are applied from mildly acidic water based solutions. Although some carbon smut deposits on annealed steel are loose and can be washed off, many are very dense and form a tenaceous skin that resists industrial cleaners. Even the acidity in the phosphating solution is not sufficient to penetrate the dense carbon deposits of smutted steel and very poor phosphate coatings are obtained. The only certain ways to remove the carbon smut sufficiently are either mechanically by surface grinding or by shot blasting, or chemically by strong acid pickling. Both such types of preparation are expensive and time consuming and often not possible to integrate in existing production lines.
We have now discovered a process for cold rolling steel sheet or strip whereby it is produced substantially free of carbon smut and/or more receptive to phosphatizing and subsequent painting by adding to the rolling oil from about 0.5 to 5% by weight of additive, based on the weight of the rolling oil and additive, of specific organic nitro compounds. The organic nitro compounds are one or more members selected from the group consisting of 2,4-dinitro benzoic acid, 2,5-dinitro benzoic acid, 3,4-dinitro benzoic acid, 3,5-dinitro benzoic acid, picric acid, 1,3-dinitro benzene, 2,4,6-trinitro toluene, 3,5-dinitro salicylic acid, 2-amino-6-nitrobenzothiazole, poly glycol ester of 3,5-dinitro benzoic acid, dimethyl octyne diol ester of 3,5-dinitro benzoic acid, 2,4,7-trinitro-9-fluorenone and 1,5-difluoro-2,4-dinitro benzene.
Following cold rolling of the steel sheet or strip in contact with the rolling oils of this invention and without further treatment, it is batch annealed. The processed steel may have additional surface treatments following annealing.
Another aspect of our invention is directed to a cold rolling lubricant composition comprising a conventional rolling oil which contains from 0.5 to 5% of one or more of the additives described above which inhibit the formation of carbon smut when the steel is batch annealed.
The rolling oil containing the smut inhibiting additive may be used undiluted in the cold rolling mill but generally it is used as an oil in water emulsion with the oil constituting from about 0.5 to 15% by weight of the combined oil and water.
The chemicals which we add to conventional rolling lubricant to inhibit the formation of carbon smut during batch annealing are one or more members selected from the group consisting of 2,4-dinitro benzoic acid, 2,5-dinitro benzoic acid, 3,4-dinitro benzoic acid, 3,5-dinitro benzoic acid, picric acid, 1,3-dinitro benzene, 2,4,6-trinitro toluene, 3,5-dinitro salicylic acid, 2-amino-6-nitrobenzothiazole, poly glycol ester of 3,5-dinitro benzoic acid, dimethyl octyne diol ester of 3,5-dinitro benzoic acid, 2,4,7-trinitro-9-fluorenone and 1,5-difluoro-2,4-dinitro benzene. The smut inhibiting additives are incorporated into the cold rolling oil in an amount ranging from about 0.5 to 5% by weight based on the combined weight of the additive and rolling oil. In some cases, we have found 0.5% of the organic nitro compound to be an effective smut inhibitor but we prefer a minimum of about 1%. Amounts greater than 5% give no increased benefit. The smut inhibiting additives as well as other additives described below are easily incorporated in the cold rolling oil by conventional liquid mixing and blending equipment.
We have found that the organic nitro compounds which are effective smut inhibitors are either soluble in the rolling oil or are soluble in the water used to prepare oil in water emulsions which are then used as the rolling lubricant.
The cold rolling oil can be any conventional rolling oil available on the market today from a large number of suppliers. Typically, the cold rolling oil will be based on a mineral oil derived from either a naphthenic or paraffinic base. The mineral oil may vary from about 0 to 95% by weight of the rolling lubricant. The mineral oil will generally have a viscosity range of 150 to 350 S.U.S. Also, the rolling lubricant will generally have present from about 0 to 95% by weight of fatty acid esters such as tallow, white or yellow grease and lard derived primarily from oleic, palmitic and stearic acid esters of glycerol. The mineral oil and fatty acid esters in total must comprise at least about 80% by weight of the cold rolling oil. Either one or any mixture of the mineral oil and fatty acid ester totalling at least about 80% by weight of the rolling lubricant is satisfactory.
Small amounts of fatty acids may also be present such as tallow fatty acids and tall oil fatty acids composed primarily of oleic, stearic or palmitic fatty acids. The fatty acids will constitute about 0 to 10% by weight of the rolling lubricant.
The cold rolling oil or lubricant may also contain from about 0.1 to 0.5% antioxidants such as 2,6 di-tertiary butyl phenol; 2,6 di-tertiary butyl 4-n-butyl phenol; 2,6 di-tertiary butyl p-cresol; 4-hydroxymethyl 2,6 di-tertiary butyl phenol; butylated hydroxytoluene or 2,2' methylenebis (4-methyl 6-tert butylphenol). Also, about 0.05 to 1.0% by weight of a bactericide such as orthophenyl phenol; 2,4,5 trichlorophenol; pentachlorophenol; o-benzyl p-chlorophenol; or hexahydro-1,3,5 tris(2-hydroxyethyl-S-triazine) is very desirable and in many cases necessary. Perfumes at a concentration of about 0.1 to 0.3% by weight and defoaming agents at a concentration of about 0.05 to 1.0% by weight may also be present. Typical defoaming agents include dimethyl silicone and dimethyl polysiloxane as well as many others of undisclosed composition.
A typical cold rolling oil or rolling lubricant will have the following composition expressed as percent by weight: mineral oil--45%, yellow grease--44%, smut inhibitor (2,4,6-trinitrotoluene)--1%, fatty acid (tallow fatty acid)--4%, emulsifier (nonylphenol ethoxylate)--5.7%, antioxidant (2.6-ditertiarybutylphenol)--0.1%, perfume--0.1%, bactericide (o-phenylphenol)--0.05% and defoamer (silicone fluid)--0.05%.
The rolling oils with the 0.5 to 5% by weight of organic nitro compound smut inhibitor may be used neat but generally for economic reasons the rolling oils are used as oil in water emulsions. The amount of rolling oil emulsified in water will vary from about 0.5 to 15% by weight based on the combined weight of the oil and water. The oil in water emulsion can be prepared by adding the rolling oil to the water in a mixing tank using a high speed stirrer. In order to prepare the oil in water emulsion it is necessary that an emulsifying agent be present in the rolling oil at a concentration of about 0.5 to 10% by weight. If desired, the emulsifying agent can be added to the water used to prepare the oil in water emulsion.
The emulsifier used in preparing the oil in water emulsion can be any conventional emulsifying agent. Typical emulsifying agents are the ethoxylated alkyl phenols in which the alkyl groups may be within the range of C8 to C18 and the moles of ethylene oxide range from 5 to 12 units. Typical ethoxylated alkyl phenols are octy phenol, nonyl phenol, dodecyl phenol and dinonyl phenol ethoxylates.
Another class of emulsifiers useful in our invention is the ethoxylated linear and branched chain primary alcohols of C8 to C16 carbon content and having about 5 to 12 moles of ethylene oxide per mole of alcohol. Tridecyl alcohol ethoxylate is an example.
Another class of emulsifiers is the ethoxylated fatty amines of C11 to C18 and having about 5 to 15 moles of ethylene oxide per mole of fatty amine. Examples of this class of emulsifier are oleyl amine, octadecyl amine and coco amine ethoxylates.
The polyethylene oxide glycol esters of C12 to C18 fatty acids having about 5 to 15 moles of ethylene oxide per mole of fatty acid are also good emulsifiers for oil in water emulsions. This class of emulsifiers includes polyoxyethylene glycol oleate (5 to 15 moles of ethylene oxide, polyoxyethylene glycol stearate (5 to 15 moles of ethylene oxide) and polyoxyethylene glycol laurate (5 to 15 moles ethylene oxide).
In order to achieve good plate-out of the rolling oil on the steel it has been found that the pH of the aqueous emulsion must be within the range of about pH 4 to 8. When acidic components are introduced into the rolling oils such as by using nitrated benzoic acid or nitrated salicylic acid smut inhibitors or by using acidic emulsifying agents an alkaline type pH modifier is required. Generally, the rolling oil will contain about 0 to 8% by weight of the pH modifier. The percent by weight of the pH modifier is determined largely by trial and error experiments.
We have found the aliphatic amines of C2 to C12 range to be satisfactory pH modifiers. Typical amines are morpholine, di-n-butylamine, di-n-propylamine and di-hexylamine; useful aromatic amines are aniline, pyridine and diphenylamine.
A typical rolling oil containing a carbon smut inhibitor together with a pH modifier has the following composition expressed as percent by weight: Blend of palmitic, stearic and oleic acid esters of glycerol--67%; paraffinic mineral oil (200 SUS)--22.9%; blends of palmitic, stearic and oleic acids (fatty acid)--5.5%; nonyl phenol ethoxylate (9 moles EO) (emulsifier)--2.2%; 3,5 dinitro benzoic acid (smut inhibitor)--1.0%; morpholine (pH modifier)--1.0%; o-phenyl phenol (biocide)--0.2%; butylated hydroxytoluene (antioxidant)--0.1%; and odor masking perfume--0.1%. (Total--100%).
Cold rolling lubricants described above containing 1 and 5% by weight respectively of the various carbon smut inhibitors were evaluated for postannealing inhibition of carbon smut by the following procedure.
Each of the rolling oil compositions as prepared in Example I is emulsified in water at 10% by volume to provide an emulsion having a concentration which will yield and oil coating weight on steel approximately equal to that obtained under production conditions. Steel test panels are dipped in each 10% emulsion until thoroughly coated and then supported vertically on paper towels until the water has evaporated, leaving an oil coating on the steel. These prepared panels are then stacked and bolted between two steel plates after which they are stored overnight at 250° F. to simulate a tightly wound steel coil from a rolling mill.
To simulate batch annealing, this stack of panels is placed in an inert gas atmosphere retort furnace of 6 liter volume. The gas used is 95% nitrogen/5% hydrogen at a flow rate of 300 cc. per minute. The steel panels were annealed in this furnace at 1250° F. for 10 hours. After cooling, the panels were observed visually.
After annealing, the panels were rated for amount of smut by visual inspection. For each variation, sets of 6 panels were prepared. Up to 11 sets could be tested in one stack. In each annealing run, one control set of oiled panels without additives was included as a control, against which the sets with additives were rated. It is not possible to attach absolute numerical values to the visual appearance, because the quality of steel as manufactured in a mill does vary enough from batch to batch, even for the same grade of steel to result in differences in appearance. We made reasonably sure that we at least used the same batch of steel for one run and judged the appearance of the sets relative to each other. The observations of smut inhibition are shown in Table I below.
The next step in the test procedure was the phosphate coating of the panels treated in Example I. This was done as follows:
The panels were cleaned in a commercial heavy duty alkaline cleaner at 200° F. temperature and of 8 oz/gal concentration by brushing and 1 minute immersion. The panels were water rinsed and spray coated 1 minute at 135° F. with a commercial zinc phosphate coating bath of 12 points concentration. Such a bath consists essentially of a water solution of about 1% of acid zinc phosphate with minor amounts of acid nickel phosphate and nitric acid, operated at a pH close to the precipitation point of tertiary zinc phosphate.
For each anneal test run, a set of non-annealed good grade of steel panels were phosphate coated and painted. Also, the panels were spray painted with about 0.0015" of a commercial high bake appliance alkyd enamel and baked according to specification.
Next, the painted surface of each panel was scored with a steel scribe down to metal by making two lines diagonally from corner to opposite corner. The panels were then placed in a salt spray cabinet and exposed to salt spray for 10 days at 95° F. and a salt concentration of 5%, according to test method ASTM B117.
After the test was finished, the panels were rated for the width of corrosion creep from the scribe line according to ASTM D1654. This specification uses a scale from 0 to 10 for judgement, 10 being a perfect score, i.e. no corrosion creep at all; 9 having traces of corrosion, 6=1/8" creep, 4=1/4" and 0 more than one inch. For all practical purposes, a rating below 6 is usually considered failing, although for some inexpensive low cost finishes, figures even as low as 4 might be acceptable. Results of 8 (1/32" creep) and higher are considered excellent.
We have found generally that annealed panels with less visual carbon deposits did result in better salt spray resistance. However, there were some additives that did not improve the appearance at all, compared to the control, but still did improve the salt spray resistance.
The smut inhibiting compounds described heretofore, all used at the 1% and the 5% level in the rolling oil, have been found to improve the appearance and/or salt spray resistance of the annealed steel. The results are presented in Table I. In Table I, each subdivision represents a different stack of steel with each stack having its own untreated (control) panel.
TABLE I(a)
__________________________________________________________________________
Appearance
Phosphate
Results
Smut Concen-
Oil Coating
after Coating
Salt Spray
Inhibitor
tration
Weight
Anneal Weight
ASTM-D 1654
Remarks
__________________________________________________________________________
None -- 145 mg/ft.sup.2
-- 290 mg/ft.sup.2
4.0 ASTM-D:
10 = perfect score,
0 = complete failure
3,5-DNBA
1% 120 mg/ft.sup.2
better than
350 mg/ft.sup.2
4.0 No pH adjustment
control
3,5-DNBA
1% 147 mg/ft.sup.2
better than
319 mg/ft.sup.2
5.0 pH adjusted with
control ammonia
3,5-DNBA
5% 146 mg/ft.sup.2
better than
370 mg/ft.sup.2
8.0 pH adjusted with
control ammonia
Picric Acid
1% 200 mg/ft.sup.2
worse than
252 mg/ft.sup.2
3.0 no pH adjustment -
control emulsion split
Picric Acid
5% 362 mg/ft.sup.2
better than
320 mg/ft.sup.2
5.0 no pH adjustment -
control emulsion split
Picric Acid
1% 137 mg/ft.sup.2
better than
323 mg/ft.sup.2
4.0 pH adjusted with
control ammonia
Picric Acid
5% 156 mg/ft.sup.2
better than
329 mg/ft.sup.2
6.5 pH adjusted with
control ammonia
__________________________________________________________________________
TABLE I(b)
__________________________________________________________________________
Appearance
Phosphate
Results
Smut Concen-
Oil Coating
after Coating
Salt Spray
Inhibitor
tration
Weight
Anneal Weight
ASTM-D 1654
Remarks
__________________________________________________________________________
None -- 120 mg/ft.sup.2
-- 257 mg/ft.sup.2
4.5 --
(control)
3,5-DNBA
1% 155 mg/ft.sup.2
better than
247 mg/ft.sup.2
7.0 pH adjusted with
control ammonia
3,5-DNBA
5% 133 mg/ft.sup.2
better than
242 mg/ft.sup.2
8.5 pH adjusted with
control ammonia
2,5-DNBA
1% 148 mg/ft.sup.2
better than
235 mg/ft.sup.2
6.0 pH adjusted with
control ammonia
2,5-DNBA
5% 139 mg/ft.sup.2
better than
308 mg/ft.sup.2
7.0 pH adjusted with
control ammonia
3,4-DNBA
1% 123 mg/ft.sup.2
like control
286 mg/ft.sup.2
4.5 pH adjusted with
ammonia
3,4-DNBA
5% 150 mg/ft.sup.2
like control
312 mg/ft.sup.2
7.0 pH adjusted with
ammonia
3,5-Dinitro
1% 137 mg/ft.sup.2
worse than
330 mg/ft.sup.2
5.0 pH adjusted with
Salicylic Acid control ammonia
3,5-Dinitro
5% 136 mg/ft.sup.2
worse than
337 mg/ft.sup.2
6.5 pH adjusted with
Salicylic Acid control ammonia
__________________________________________________________________________
**DNBA = dinitrobenzoic acid**
TABLE I(c)
__________________________________________________________________________
Appearance
Phosphate
Results
Smut Concen-
Oil Coating
after Coating
Salt Spray
Inhibitor
tration
Weight
Anneal Weight
ASTM D-1654
Remarks
__________________________________________________________________________
None -- 128 mg/ft.sup.2
-- 310 mg/ft.sup.2
4.0 --
(control)
3,5-DNBA
1% 136 mg/ft.sup.2
better than
332 mg/ft.sup.2
7.5 pH adjusted with
control ammonia
3,5-DNBA
5% 135 mg/ft.sup.2
better than
332 mg/ft.sup.2
8.5 pH adjusted with
control ammonia
2,4-dinitro
1% 140 mg/ft.sup.2
better than
287 mg/ft.sup.2
6.5 pH adjusted with
phenol control ammonia
2,4-dinitro
5% 131 mg/ft.sup.2
better than
302 mg/ft.sup.2
8.0 pH adjusted with
phenol control ammonia
2,4,6-trinitro
1% 117 mg/ft.sup.2
better than
284 mg/ft.sup.2
8.5 --
toluene control
2,4,6-trinitro
5% 131 mg/ft.sup.2
better than
245 mg/ft.sup.2
6.0 --
toluene control
2-amino-6-
1% 136 mg/ft.sup.2
better than
241 mg/ft.sup.2
8.5 --
nitrobenzo- control
thiazole
2-amino-6-
1% 152 mg/ft.sup.2
worse than
246 mg/ft.sup.2
9.0 Appearance after an-
nitrobenzo- control neal worst of this
thiazole run. However, surface
structure apparently
was modified in such
a way that salt spray
performance was best.
__________________________________________________________________________
**DNBA = dinitrobenzoic acid**
TABLE I(d)
__________________________________________________________________________
Appearance
Phosphate
Results
Smut Concen-
Oil Coating
after Coating
Salt Spray
Inhibitor
tration
Weight
Anneal Weight
ASTM-D 1654
Remarks
__________________________________________________________________________
None -- 133 mg/ft.sup.2
-- 337 mg/ft.sup.2
4.0 --
(control)
2,4,6-trinitro
1% 136 mg/ft.sup.2
better than
383 mg/ft.sup.2
6.0 --
toluene control
2,4,6-trinitro
5% 137 mg/ft.sup.2
better than
352 mg/ft.sup.2
8.5 --
toluene control
Polyglycol ester
1% 146 mg/ft.sup.2
Like content
316 mg/ft.sup.2
4.0 --
of 3,5-DNBA
(Carbowax 500
ester)
Polyglycol ester
5% better than
314 mg/ft.sup.2
6.5 --
of 3,5-DNBA control
(Carbowax 500
ester)
Dimethyl octyne
1% 146 mg/ft.sup.2
worse than
323 mg/ft.sup.2
3.5 --
diol ester of control
3,5-DNBA
Dimethyl octyne
5% 145 mg/ft.sup.2
worse than
296 mg/ft.sup.2
8.0 --
diol ester of control
3,5-DNBA
__________________________________________________________________________
**DNBA = dinitrobenzoic acid**
TABLE I(e)
__________________________________________________________________________
Appearance
Phosphate
Results
Smut Concen-
Oil Coating
after Coating
Salt Spray
Inhibitor
tration
Weight
Anneal Weight
ASTM D-1654
Remarks
__________________________________________________________________________
None -- 116 mg/ft.sup.2
-- 227 mg/ft.sup.2
5.5 --
(control)
2,4-DNBA
1% 134 mg/ft.sup.2
better than
257 mg/ft.sup.2
8.5 pH adjusted
control with ammonia
2,4-DNBA
5% 129 mg/ft.sup.2
better than
269 mg/ft.sup.2
9.5 pH adjusted
control with ammonia
2,5-DNBA
1% 126 mg/ft.sup.2
better than
275 mg/ft.sup.2
9.0 pH adjusted
control with ammonia
2,5-DNBA
5% 117 mg/ft.sup.2
worse than
275 mg/ft.sup.2
9.0 pH adjusted*
control with ammonia
3,4-DNBA
1% 112 mg/ft.sup.2
worse than
288 mg/ft.sup.2
8.0 pH adjusted*
control with ammonia
3,4-DNBA
5% 137 mg/ft.sup.2
worse than
292 mg/ft.sup.2
8.5 pH adjusted*
control with ammonia
3,5-DNBA
1% 127 mg/ft.sup.2
worse than
248 mg/ft.sup.2
8.0 pH adjusted*
control with ammonia
3,5-DNBA
5% 117 mg/ft.sup.2
worse than
278 mg/ft.sup.2
9.0 pH adjusted*
control with ammonia
__________________________________________________________________________
*good salt spray performance in spite of poor appearance after anneal
**DNBA = dinitrobenzoic acid**
TABLE I(f)
__________________________________________________________________________
Appearance
Phosphate
Results
Smut Concen-
Oil Coating
after Coating
Salt Spray
Inhibitor
tration
Weight
Anneal Weight
ASTM D-1654
Remarks
__________________________________________________________________________
None -- 188 mg/ft.sup.2
-- 312 mg/ft.sup.2
3.5 --
(control)
2,4,6-trinitro
5 107 mg/ft.sup.2
better than
351 mg/ft.sup.2
6.0 --
toluene control
2,4,6-trinitro
5% 210 mg/ft.sup.2
worse than
356 mg/ft.sup.2
6.5 --
toluene control
1,5-difluoro-
1% 84 mg/ft.sup.2
worse than
326 mg/ft.sup.2
5.0 --
2,4-dinitro- control
benzene
1,5-difluoro-
5% 118 mg/ft.sup.2
like control
322 mg/ft.sup.2
6.0 --
2,4-dinitro-
benzene
3,5-DNBA
1% 387 mg/ft.sup.2
worse than
392 mg/ft.sup.2
3+ Laboratory technician
control overheated the oil
after the smut in-
hibitor was added,
resulting in sub-
standard performance
3,5-DNBA
5% 187 mg/ft.sup.2
worse than
416 mg/ft.sup.2
3.5+ Laboratory technician
overheated the oil
after the smut in-
hibitor was added,
resulting in sub-
standard performance
__________________________________________________________________________
**DNBA = dinitrobenzoic acid**
TABLE I(g)
__________________________________________________________________________
Appearance
Phosphate
Results
Smut Concen-
Oil Coating
after Coating
Salt Spray
Inhibitor
tration
Weight
Anneal Weight
ASTM D-1654
Remarks
__________________________________________________________________________
None -- 118 mg/ft.sup.2
-- 388 mg/ft.sup.2
3.0 --
(control)
2,4,6-trinitro
1% 176 mg/ft.sup.2
better than
369 mg/ft.sup.2
5.5- --
toluene control
2,4,6-trinitro
5% 180 mg/ft.sup.2
worse than
314 mg/ft.sup.2
5.5 --
toluene control
2,4,7-trinitro-
1% 123 mg/ft.sup.2
worse than
500 mg/ft.sup.2
4.0 --
9-fluorenone control
2,4,7-trinitro-
5% 182 mg/ft.sup.2
worse than
284 mg/ft.sup.2
6.0 --
9-fluorenone control
__________________________________________________________________________
Claims (8)
1. In a process for producing steel sheet or strip substantially free of carbon smut deposits from cold rolled steel sheet or strip the improvement comprising cold rolling the steel sheet or strip in contact with a rolling oil containing about 0.5 to 5% by weight of one or more organic nitro-compounds selected from the group consisting of 2,4-dinitro benzoic acid, 2,5-dinitro benzoic acid, 3,4-dinitro benzoic acid, 3,5-dinitro benzoic acid, picric acid, 1,3-dinitro benzene, 2,4,6-trinitro toluene, 3,5-dinitro salicylic acid, 2-amino-6- nitrobenzothiazole, poly glycol ester of 3,5-dinitro benzoic acid, dimethyl octyne diol ester of 3,5-dinitro benzoic acid, 2,4,7-trinitro-9-fluorenone and 1,5-difluoro-2,4-dinitro benzene and thereafter without further treatment batch annealing the steel strip.
2. The process of claim 1 in which the amount of the organic nitro compound carbon smut inhibitor in the rolling oil ranges from about 1 to 5% by weight based on the mixture of organic nitro compound and rolling oil.
3. The process of claim 1 in which the rolling oil containing the organic nitro compound carbon smut inhibitor is emulsified in water.
4. The process of claim 3 in which the rolling oil comprises 2 to 20% by weight of the mixture of rolling oil and water.
5. The process of claim 1 in which a pH modifier is present in the rolling oil at a concentration of 0 to 8% by weight.
6. The process of claim 1 in which an aliphatic amine of C2 to C12 content is present in the rolling oil at a concentration of 0 to 8% by weight to control acidity.
7. A rolling lubricant for cold rolling steel sheet or strip comprising a rolling oil containing from 0.5 to 5% by weight of one or more members selected from the group consisting of 2,4-dinitro benzoic acid, 2,5-dinitro benzoic acid, 3,4-dinitro benzoic acid, 3,5-dinitro benzoic acid, picric acid, 1,3-dinitro benzene, 2,4,6-trinitro toluene, 3,5-dinitro salicylic acid, 2-amino-6-nitrobenzothiazole, poly glycol ester of 3,5-dinitro benzoic acid, dimethyl octyne diol ester of 3,5-dinitro benzoic acid, 2,4,7-trinitro-9-fluorenone and 1,5-difluoro-2,4-dinitro benzene.
8. An aqueous emulsion of the rolling lubricant of claim 7 at a concentration of 0.5 to 15% by weight of rolling lubricant based on the combined weight of rolling lubricant and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/255,605 US4346014A (en) | 1981-04-20 | 1981-04-20 | Rolling oil compositions and method of inhibiting carbon smut on batch annealed steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/255,605 US4346014A (en) | 1981-04-20 | 1981-04-20 | Rolling oil compositions and method of inhibiting carbon smut on batch annealed steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4346014A true US4346014A (en) | 1982-08-24 |
Family
ID=22969079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/255,605 Expired - Lifetime US4346014A (en) | 1981-04-20 | 1981-04-20 | Rolling oil compositions and method of inhibiting carbon smut on batch annealed steel |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4346014A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908072A (en) * | 1987-09-10 | 1990-03-13 | Nippon Mining Co., Ltd. | In-process formation of hard surface layer on Ti/Ti alloy having high resistance |
| US20060281646A1 (en) * | 2003-03-03 | 2006-12-14 | Oleksiak Thomas P | Additive for cold rolling lubricants |
| WO2011117892A2 (en) | 2010-03-25 | 2011-09-29 | Indian Oil Corporation Ltd. | Composition of oil for high speed thin and thick gauge steel sheet rolling in tandem mills |
| US20120244373A1 (en) * | 2009-11-24 | 2012-09-27 | Sumitomo Electric Industries, Ltd. | Method for producing magnesium alloy sheet and magnesium alloy coil stock |
| CN109233972A (en) * | 2018-11-13 | 2019-01-18 | 无锡市高润杰化学有限公司 | A kind of steel cold-rolled lubricating oil with excellent annealing cleanness |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2066173A (en) * | 1934-04-24 | 1936-12-29 | Du Pont | Lubricant |
| US3265620A (en) * | 1963-08-29 | 1966-08-09 | Donald K Heiman | Cutting fluid |
| US3267037A (en) * | 1963-05-27 | 1966-08-16 | Phillips Petroleum Co | Process for lubricating metal surfaces during working of the same |
| US3632487A (en) * | 1969-09-30 | 1972-01-04 | Pennwalt Corp | Method of preparing tinplate |
| US3779818A (en) * | 1971-04-01 | 1973-12-18 | Bethlehem Steel Corp | Method for preventing the formation of rust on the surface of coiled steel strip and an inhibitor for accomplishing same |
| US3907612A (en) * | 1974-02-15 | 1975-09-23 | Pennwalt Corp | Preanneal rinse process for inhibiting pin point rust |
| US4062784A (en) * | 1975-08-05 | 1977-12-13 | Swiss Aluminium Ltd. | Oil-in-water emulsion for cold rolling |
| US4214924A (en) * | 1978-10-27 | 1980-07-29 | Pennwalt Corporation | Method of improving surface characteristic of heat-treated metal |
-
1981
- 1981-04-20 US US06/255,605 patent/US4346014A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2066173A (en) * | 1934-04-24 | 1936-12-29 | Du Pont | Lubricant |
| US3267037A (en) * | 1963-05-27 | 1966-08-16 | Phillips Petroleum Co | Process for lubricating metal surfaces during working of the same |
| US3265620A (en) * | 1963-08-29 | 1966-08-09 | Donald K Heiman | Cutting fluid |
| US3632487A (en) * | 1969-09-30 | 1972-01-04 | Pennwalt Corp | Method of preparing tinplate |
| US3779818A (en) * | 1971-04-01 | 1973-12-18 | Bethlehem Steel Corp | Method for preventing the formation of rust on the surface of coiled steel strip and an inhibitor for accomplishing same |
| US3907612A (en) * | 1974-02-15 | 1975-09-23 | Pennwalt Corp | Preanneal rinse process for inhibiting pin point rust |
| US4062784A (en) * | 1975-08-05 | 1977-12-13 | Swiss Aluminium Ltd. | Oil-in-water emulsion for cold rolling |
| US4214924A (en) * | 1978-10-27 | 1980-07-29 | Pennwalt Corporation | Method of improving surface characteristic of heat-treated metal |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908072A (en) * | 1987-09-10 | 1990-03-13 | Nippon Mining Co., Ltd. | In-process formation of hard surface layer on Ti/Ti alloy having high resistance |
| US20060281646A1 (en) * | 2003-03-03 | 2006-12-14 | Oleksiak Thomas P | Additive for cold rolling lubricants |
| US20120244373A1 (en) * | 2009-11-24 | 2012-09-27 | Sumitomo Electric Industries, Ltd. | Method for producing magnesium alloy sheet and magnesium alloy coil stock |
| US9604267B2 (en) * | 2009-11-24 | 2017-03-28 | Sumitomo Electric Industries, Ltd. | Method for producing magnesium alloy sheet and magnesium alloy coil stock |
| WO2011117892A2 (en) | 2010-03-25 | 2011-09-29 | Indian Oil Corporation Ltd. | Composition of oil for high speed thin and thick gauge steel sheet rolling in tandem mills |
| CN109233972A (en) * | 2018-11-13 | 2019-01-18 | 无锡市高润杰化学有限公司 | A kind of steel cold-rolled lubricating oil with excellent annealing cleanness |
| CN109233972B (en) * | 2018-11-13 | 2021-10-29 | 无锡市高润杰化学有限公司 | A steel cold rolling oil with excellent annealing detergency |
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